EP1203041B1 - Method for producing modified polycarbonates - Google Patents

Method for producing modified polycarbonates Download PDF

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Publication number
EP1203041B1
EP1203041B1 EP00951347A EP00951347A EP1203041B1 EP 1203041 B1 EP1203041 B1 EP 1203041B1 EP 00951347 A EP00951347 A EP 00951347A EP 00951347 A EP00951347 A EP 00951347A EP 1203041 B1 EP1203041 B1 EP 1203041B1
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Prior art keywords
hydroxyphenyl
bis
mol
bisphenol
process according
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German (de)
French (fr)
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EP1203041A1 (en
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Silke Kratschmer
Uwe Hucks
Lothar Bunzel
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Covestro Deutschland AG
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Bayer MaterialScience AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/307—General preparatory processes using carbonates and phenols

Definitions

  • the present invention is a melt transesterification process for the production of polycarbonates.
  • the object was thus to find a melt transesterification process which allows the production of polycarbonates whose end groups consist in part of other phenols than phenol itself, wherein as much of the chain terminator used should be incorporated.
  • the object has been achieved by a process for preparing polycarbonates from a single bisphenol, preferably from bisphenol A, and a carbonic acid diester, in the presence of a phenol suitable as a chain terminator, wherein the phenol used as a chain terminator can be used in free form or as a transesterifiable under the synthesis conditions, characterized in that phosphonium salts are used as the catalyst, and 80% or more of the used as a chain terminator phenol are incorporated into the polycarbonate.
  • Sodium-ion catalysts may include hydroxides, bicarbonates, carbonates, alcoholates, acetates, boronates, hydrogen phosphates and hydrides, preferably hydroxides and alkoxides, more preferably the sodium salts of the phenols and bisphenols as they are mentioned under bisphenols and chain terminators and the Sodium salt of phenol itself, most preferably the sodium salt of 2,2-bis (4-hydroxyphenyl) propane can be used.
  • the chain terminator is preferably added as alkylphenol at 0.4 to 17 mol%, preferably 1.3 to 8.6 mol% (based on the dihydroxy compound). In this case, the addition can take place both before the reaction and completely or partially during the reaction.
  • Dihydroxy compounds in the context of the process according to the invention are those of the formula (VI) HO-Z-OH (VI) in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridge members.
  • the inventive method is generally carried out at temperatures between 75 ° C to 325 ° C and pressures of 1 bar to 0.01 mbar.
  • the implementation of the method according to the invention is carried out, for example, such that in the first stage, the melting of the diphenols, the carbonic diester, the Catalyst and optionally the alkylphenols and branching agents at temperatures from 75 ° C to 225 ° C, preferably from 105 ° C to 235 ° C, more preferably from 120 ° C to 190 ° C, under normal pressure in 0.1 to 5 hours, preferably in 0.25 to 3 hours. Then, by applying a vacuum and raising the temperature by distilling off the monophenol, the oligocarbonate is prepared. In the last step, the polycarbonate is prepared by further increasing the temperature to 240 ° C to 325 ° C and at a pressure of ⁇ 2 mbar in the polycondensation.
  • the process according to the invention can be carried out both continuously and discontinuously, for example in stirred vessels, thin-film evaporators, stirred tank cascades, extruders, kneaders, simple disk reactors or high-viscosity reactors.
  • the isolation of the polycarbonates obtainable according to the invention takes place, for example, by discharging, spinning and granulation.
  • the polycarbonates obtainable by the process according to the invention may have weight average molecular weights M w between about 2,000 and 150,000, preferably between about 4,500 and 55,000, wherein M w is determined by the relative solution viscosity in dichloromethane or mixtures of equal amounts by weight phenol / o-dichlorobenzene wherein the calibration is done by light scattering.
  • the polycarbonates obtainable according to the invention have the usual OH end group contents known from the literature, which can be determined photometrically with titanium tetrachloride.
  • the polycarbonates produced by the process of the invention show good mechanical properties, high transparency and are free of solvents.
  • the incorporation of the alkylphenols used was determined by 13 C for cumylphenol, and by 1 H-NMR spectroscopy for the other alkylphenols. That became calculated how many percent of the chain terminator used was present in the polycarbonate as an end group.
  • auxiliaries and reinforcing materials can be added to the polycarbonates prepared according to the invention.
  • stabilizers As alkyl and aryl phosphites, phosphates, phosphanes, low molecular weight carboxylic acid esters, halogen compounds, salts, chalk, quartz powder, glass and carbon fibers, pigments and combinations thereof.
  • the erfindungsmä field polycarbonates and other polymers can be admixed, for.
  • polyolefins polyurethanes, polyesters and polystyrene.
  • polycarbonates obtainable by the process according to the invention can be processed on conventional machines, for example on extruders or injection molding machines to form any shaped articles, for example into films or plates in a conventional manner.
  • the temperature is raised to 190 ° C and the vacuum to 100 mbar and the resulting phenol distilled off. After 20 minutes, the temperature is increased to 235 ° C and the vacuum improved to 60 mbar. After 15 minutes, the temperature is raised to 250 ° C and after a further 15 minutes, the vacuum to 5 mbar. The mixture is then heated to 280 ° C and the pressure after 15 minutes reduced to 0.5 mbar. After another 15 minutes, stirred at 300 ° C for another 30 minutes. The results are summarized in Table 1.
  • Example 2 As Example 1, but it is dispensed with the addition of boric acid. The results are summarized in Table 2.
  • Example 3 only 45.84 g (107 mol% based on bisphenol A) diphenyl carbonate and 1.22 g (2 mol% based on bisphenol A) of 3-pentadecylphenol instead of 4-phenoxyphenol weighed.
  • Example 3 only 45.41 g (106 mol% based on bisphenol A) of diphenyl carbonate and instead of 4-phenoxyphenol 3.32 g (5 mol% based on bisphenol A) Cumylphenylphenylcarbonate weighed.
  • Table 2 ⁇ / u> example solution viscosity used alkylphenol [mol%] Found alkylphenol [mol%] Incorporation of the alkylphenol [%] 1 1,134 5 4.0 80 2 1,160 5 4.2 84 3 1,158 4 3.2 80 4 1,161 2 2.0 100 5 1,113 5 4.2 84

Abstract

A process for the synthesis of polycarbonate is disclosed. The process entails reacting in the presence of at least one phosphonium salt as catalyst, at least one diphenol, at least one carbonic acid diester, and at least one alkyl group-substituted phenol chain terminator. The chain terminator is introduced in free form or as a transesterifiable compound under the conditions of the synthesis. The polycarbonate thus produced is suitable for preparing a variety of molded articles.

Description

Gegenstand der vorliegenden Erfindung ist ein Schmelzeumesterungsverfahren zur Herstellung von Polycarbonaten.The present invention is a melt transesterification process for the production of polycarbonates.

Die Herstellung von aromatischen Polycarbonaten nach dem Schmelzeumesterungsverfahren ist literaturbekannt und beispielsweise in der Encyclopedia of Polymer Science, Vol. 10 (1969 ), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964 ) sowie ausgehend von der DE 1 031 512 in einigen Patenten beschrieben. Das Patent EP 360 578 zeigt, daß die Endgruppen eines Polycarbonates, das über Schmelzeumesterung hergestellt wurde, durch Zugabe eines Kettenabbrechers ausgetauscht werden können. Es zeigt sich jedoch, daß jeweils nur ein Teil der Menge an eingesetztem Kettenabbrecher wirklich im Polycarbonat als Endgruppe verbleibt. Da die Mechanik, insbesondere Kettenabbrecher-reicher PC-Typen, insbesondere niedermolekularer und verzweigter PC-Typen, deutlich von den Endgruppen beeinflußt wird, ist ein möglichst vollständiger Ersatz der Phenol-Endgruppen durch andere geeignetere Phenole wünschenswert. Daneben wird das bei der Polykondensation entstehende Phenol bei der Entfernung aus dem Prozeß durch Destillation mit dem Kettenabbrecher verunreinigt, wenn dieser nicht vollständig eingebaut wird. Ein möglichst vollständiger Einbau ist also nicht nur für eine hohe Reaktionsausbeute, sondern auch in Hinsicht auf die Wiederverwendung des abdestillierten Phenols anzustreben.The preparation of aromatic polycarbonates after the melt transesterification process is known from the literature and is described, for example, in US Pat Encyclopedia of Polymer Science, Vol. 10 (1969 ) Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964 ) and from the DE 1 031 512 described in some patents. The patent EP 360 578 shows that the end groups of a polycarbonate prepared by melt transesterification can be exchanged by adding a chain terminator. It turns out, however, that only a portion of the amount of chain terminator used really remains in the polycarbonate as an end group. Since the mechanics, in particular chain terminator-rich PC types, in particular low molecular weight and branched PC types, are clearly influenced by the end groups, the most complete possible replacement of the phenol end groups by other more suitable phenols is desirable. In addition, the phenol resulting from the polycondensation is contaminated by removal from the process by distillation with the chain terminator if it is not fully incorporated. The most complete possible incorporation is therefore not only desirable for a high reaction yield, but also with regard to the reuse of the distilled phenol.

Die Aufgabe bestand also darin, ein Schmelzeumsterungsverfahren zu finden, das die Produktion von Polycarbonaten ermöglicht, deren Endgruppen teilweise aus anderen Phenolen bestehen als Phenol selbst, wobei möglichst viel des eingesetzten Kettenabbrechers eingebaut werden sollte.The object was thus to find a melt transesterification process which allows the production of polycarbonates whose end groups consist in part of other phenols than phenol itself, wherein as much of the chain terminator used should be incorporated.

Die Aufgabe wurde gelöst durch ein Verfahren zur Herstellung von Polycarbonaten aus einem einzigen Bisphenol, bevorzugt aus Bisphenol A, und einem Kohlensäurediester, in Gegenwart eines als Kettenabbrecher geeigneten Phenols, wobei das als Kettenabbrecher verwendete Phenol in freier Form oder als unter den Synthesebedingungen umesterungsfähige Verbindung eingesetzt werden kann, dadurch gekennzeichnet, daß als Katalysator Phosphoniumsalze verwendet werden, und 80% oder mehr des als Kettenabbrecher eingesetzten Phenols ins Polycarbonat eingebaut werden.The object has been achieved by a process for preparing polycarbonates from a single bisphenol, preferably from bisphenol A, and a carbonic acid diester, in the presence of a phenol suitable as a chain terminator, wherein the phenol used as a chain terminator can be used in free form or as a transesterifiable under the synthesis conditions, characterized in that phosphonium salts are used as the catalyst, and 80% or more of the used as a chain terminator phenol are incorporated into the polycarbonate.

Phosphoniumsalze im Sinne des erfindungsgemäßen Verfahrens sind solche der Formel (I),

Figure imgb0001

  • wobei R1-4 dieselben oder verschiedene C1-C18-Alkyle, C6-C14-Aryle, C7-C12-Aralkyle oder C5-C6-Cycloalkyle sein können, bevorzugt Methyl oder C6-C14-Aryle, besonders bevorzugt Methyl oder Phenyl, und X- ein Anion wie Sulfat, Hydrogensulfat, Hydrogencarbonat, Carbonat, Acetat, Boranat, Hydrogenphosphate, ein Halogenid, bevorzugt Fluorid, Chlorid oder Bromid, ein Alkoholat der Formel OR sein kann, wobei R C6-C14-Aryl, C7-C12-Aralkyl, beovrzugt Phenyl ist. Bevorzugte Katalysatoren sind
  • Tetraphenylphosphoniumfluorid,
  • Tetraphenylphosphoniumtetraphenylboranat,
  • besonders bevorzugt Tetraphenylphosphoniumphenolat.
Phosphonium salts in the context of the process according to the invention are those of the formula (I)
Figure imgb0001
  • where R 1-4 may be the same or different C 1 -C 18 -alkyls, C 6 -C 14 -aryls, C 7 -C 12 -aralkyls or C 5 -C 6 -cycloalkyls, preferably methyl or C 6 -C 14 -Aryle, particularly preferably methyl or phenyl, and X - may be an anion such as sulfate, hydrogensulfate, bicarbonate, carbonate, acetate, boronate, hydrogen phosphates, a halide, preferably fluoride, chloride or bromide, an alcoholate of the formula OR, wherein RC 6 C 14 aryl, C 7 -C 12 aralkyl, is preferably phenyl. Preferred catalysts are
  • Tetraphenylphosphoniumfluorid,
  • Tetraphenylphosphoniumtetraphenylboranat,
  • particularly preferably tetraphenylphosphonium phenolate.

Natrium-Ionen-Katalysatoren können Hydroxide, Hydrogencarbonate, Carbonate, Alkoholate, Acetate, Boranate, Hydrogenphosphate und Hydride, bevorzugt Hydroxide und Alkoholate, besonders bevorzugt die Natriumsalze der Phenole und Bisphenole wie sie unter Bisphenolen und Kettenabbrechern erwähnt werden und das Natriumsalz von Phenol selbst, ganz besonders bevorzugt das Natriumsalz von 2,2-Bis-(4-hydroxyphenyl)-propan eingesetzt werden.Sodium-ion catalysts may include hydroxides, bicarbonates, carbonates, alcoholates, acetates, boronates, hydrogen phosphates and hydrides, preferably hydroxides and alkoxides, more preferably the sodium salts of the phenols and bisphenols as they are mentioned under bisphenols and chain terminators and the Sodium salt of phenol itself, most preferably the sodium salt of 2,2-bis (4-hydroxyphenyl) propane can be used.

Als Kettenabbrecher geeignete Alkylphenole im Sinne des erfindungsgemäßen Verfahrens sind solche der Formel (II),

Figure imgb0002

  • wobei R, R' und R" unabhängig voneinander H, gegebenenfalls verzweigte C1-C34-Alkyl/Cycloalkyl, C7-C34-Alkaryl oder C6-C34-Aryl darstellen können, beispielsweise
  • o-n-Butylphenol, m-n-Butylphenol, p-n-Butylphenol,
  • o-Isobutylphenol, m-Isobutylphenol, p-Isobutylphenol,
  • o-tert-Butylphenol, m-tert-Butylphenol, p-tert-Butylphenol,
  • o-n-Pentylphenol, m-n-Pentylphenol, p-n-Pentylphenol,
  • o-n-Hexylphenol, m-n-Hexylphenol, p-n-Hexylphenol,
  • o-Cyclohexylphenol, m-Cyclohexylphenol, p-Cyclohexylphenol,
  • o-Phenylphenol, m-Phenylphenol, p-Phenylphenol,
  • o-Isooctylphenol, m-Isooctylphenol, p-Isooctylphenol,
  • o-n-Nonylphenol, m-n-Nonylphenol, p-n-Nonylphenol,
  • o-Cumylphenol, m-Cumylphenol, p-Cumylphenol,
  • o-Naphthylphenol, m-Naphthylphenol. p-Naphthylphenol,
  • 2,5-Di-tert-Butylphenol, 2,4-Di-tert-Butylphenol, 3,5-Di-tert-Butylphenol,
  • 2,5-Dicumylphenol, 3,5-Dicumylphenol,
  • 4-Phenoxyphenol, 2-Phenoxyphenol, 3-Phenoxyphenol
  • 3-Pentadecylphenol, 2-Pentadecylphenol, 4-Pentadecylphenol,
  • 2-Phenylphenol, 3-Phenylphenol, 4-Phenylphenol,
  • Tritylphenol, 3-Triphenylmethylphenol, 2-Triphenylmethylphenol,
  • weiterhin Benzotriazolderivate der allgemeinen Formel (III)
    Figure imgb0003
     mit der obigen Bedeutung von R, R' und R" für Ra- Rf und Chromanverbindungen wie
    Figure imgb0004
     bevorzugt schwersiedende Phenole wie Tritylphenol, Cumylphenol, Phenoxyphenol, Pentadecylphenol oder Chromane,
    oder auch als unter den Synthesebedingungen umesterungsfähige Verbindungen wie z. B. Carbonate, Oxalate, o-Carbonsäureester o. ä., bevorzugt sind die freien Phenole oder die Kohlensäurediester der Formel (IV)
    Figure imgb0005
     und Formel (V),
    Figure imgb0006
     wobei R,R' und R" denen der Formel (II) entsprechen. Phenole oder umesterungsaktive Substanzen können einzeln oder im Gemisch der Synthese zugesetzt werden. Bevorzugte Mischungen sind solche mit Diphenylcarbonat. Nach dem erfindungsgemäßen Verfahren besteht die Möglichkeit, das Phenol oder die phenoltragende Verbindung zu jedem Zeitpunkt der Reaktion zuzugeben, bevorzugt zu Beginn der Reaktion, und die Zugabe kann in mehrere Protionen aufgeteilt werden. Der gesamte Anteil an Kohlensäureester beträgt 100 - 130 mol%, bevorzugt 103 - 120 mol%, bezogen auf die Dihydroxyverbindung.
Alkylphenols suitable as chain terminators in the context of the process according to the invention are those of the formula (II)
Figure imgb0002
  • where R, R 'and R "independently of one another may represent H, optionally branched C 1 -C 34 -alkyl / cycloalkyl, C 7 -C 34 -alkaryl or C 6 -C 34 -aryl, for example
  • on-butylphenol, mn-butylphenol, pn-butylphenol,
  • o-isobutylphenol, m-isobutylphenol, p-isobutylphenol,
  • o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol,
  • on-pentylphenol, mn-pentylphenol, pn-pentylphenol,
  • on-hexylphenol, mn-hexylphenol, pn-hexylphenol,
  • o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol,
  • o-phenylphenol, m-phenylphenol, p-phenylphenol,
  • o-isooctylphenol, m-isooctylphenol, p-isooctylphenol,
  • on-nonylphenol, mn-nonylphenol, pn-nonylphenol,
  • o-cumylphenol, m-cumylphenol, p-cumylphenol,
  • o-naphthylphenol, m-naphthylphenol. p-Naphthylphenol,
  • 2,5-di-tert-butylphenol, 2,4-di-tert-butylphenol, 3,5-di-tert-butylphenol,
  • 2,5-dicumylphenol, 3,5-dicumylphenol,
  • 4-phenoxyphenol, 2-phenoxyphenol, 3-phenoxyphenol
  • 3-pentadecylphenol, 2-pentadecylphenol, 4-pentadecylphenol,
  • 2-phenylphenol, 3-phenylphenol, 4-phenylphenol,
  • Tritylphenol, 3-triphenylmethylphenol, 2-triphenylmethylphenol,
  • Benzotriazole derivatives of general formula (III)
    Figure imgb0003
     with the above meaning of R, R 'and R "for R a - R f and chroman compounds such as
    Figure imgb0004
     preferably high-boiling phenols such as tritylphenol, cumylphenol, phenoxyphenol, pentadecylphenol or chromans,
    or as under the synthesis conditions transesterifiable compounds such. As carbonates, oxalates, o-carboxylic acid ester o. Ä., Preferably, the free phenols or the carbonic acid diester of the formula (IV)
    Figure imgb0005
     and formula (V),
    Figure imgb0006
     where R, R 'and R''correspond to those of the formula (II) Phenols or transesterification substances can be added individually or in a mixture of the synthesis Preferred mixtures are those with diphenyl carbonate The process according to the invention makes it possible to use the phenol or the phenol-carrying Compound at any point in the reaction, preferably at the beginning of the reaction, and the addition can be divided into several protions The total amount of carbonic acid ester is 100-130 mol%, preferably 103-120 mol%, based on the dihydroxy compound.

Für die Herstellung von Polycarbonaten nach dem erfindungsgemäßen Verfahren wird der Kettenabbrecher bevorzugt als Alkylphenol zu 0,4 - 17 mol%, bevorzugt 1,3 - 8,6 mol% (bezogen auf die Dihydroxyverbindung) zugegeben. Dabei kann die Zugabe sowohl vor der Reaktion als auch ganz oder teilweise während der Reaktion erfolgen.For the production of polycarbonates by the process according to the invention, the chain terminator is preferably added as alkylphenol at 0.4 to 17 mol%, preferably 1.3 to 8.6 mol% (based on the dihydroxy compound). In this case, the addition can take place both before the reaction and completely or partially during the reaction.

Dihydroxyverbindungen im Sinne des erfindungsgemäßen Verfahrens sind solche der Formel (VI)

        HO-Z-OH     (VI)

in denen Z ein aromatischer Rest mit 6 bis 30 C-Atomen ist, der einen oder mehrere aromatische Kerne enthalten kann, substituiert sein kann und aliphatische oder cycloaliphatische Reste bzw. Alkylaryle oder Heteroatome als Brückenglieder enthalten kann.Dihydroxy compounds in the context of the process according to the invention are those of the formula (VI)

HO-Z-OH (VI)

in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridge members.

Beispiele für Dihydroxyverbindungen der Formel (VI) sind

  • Hydrochinon,
  • Resorcin,
  • Dihydroxydiphenyle,
  • Bis-(hydroxyphenyl)-alkane,
  • Bis-(hydroxyphenyl)-cycloalkane,
  • Bis-(hydroxyphenyl)-sulfide,
  • Bis-(hydroxyphenyl)-ether,
  • Bis-(hydroxyphenyl)-ketone,
  • Bis-(hydroxyphenyl)-sulfone,
  • Bis-(hydroxyphenyl)-sulfoxide,
  • α,α'- Bis-(hydroxyphenyl)-diisopropylbenzole
sowie deren kernalkylierte und kernhalogenierte Verbindungen.Examples of dihydroxy compounds of the formula (VI) are
  • Hydroquinone,
  • resorcinol,
  • dihydroxydiphenyls,
  • Bis (hydroxyphenyl) alkanes,
  • Bis- (hydroxyphenyl) -cycloalkanes,
  • Bis (hydroxyphenyl) sulfides,
  • Bis (hydroxyphenyl) ether,
  • ketones, bis- (hydroxyphenyl),
  • sulfones bis- (hydroxyphenyl),
  • Bis (hydroxyphenyl) sulfoxides,
  • α, α'-bis (hydroxyphenyl) diisopropylbenzenes
and their nuclear alkylated and nuclear halogenated compounds.

Diese und weitere geeignete andere Diphenole sind z. B. in den US-PS 3 028 365 , 3 148 172 , 3 275 601 , 2 991 273 , 3 271 367 , 3 062 781 , 2 970 131 und 2 999 846 , in den deutschen Offenlegungsschriften 1 570 703 , 2 063 050 , 2 063 052 , 2 211 0956 , der französischen Patentschrift 1 561 518 und in der Monographie "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" beschrieben.These and other suitable other diphenols are for. Tie U.S. Patent 3,028,365 . 3 148 172 . 3,275,601 . 2 991 273 . 3 271 367 . 3 062 781 . 2,970,131 and 2,999,846 , in the German publications 1 570 703 . 2 063 050 . 2 063 052 . 2 211 0956 , the French patent 1 561 518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964".

Bevorzugte Diphenole sind beispielsweise:

  • 4,4'-Dihydroxydiphenyl,
  • 2,2-Bis-(4-hydroxyphenyl)propan,
  • 2,4-Bis-(4-hydroxyphenyl)-2-methylbutan,
  • 1,1-Bis-(4-hydroxyphenyl)cyclohexan,
  • 1,1-Bis-(4-hydroxyphenyl)-4-methylcyclohexan,
  • α,α'- Bis-(4-hydroxyphenyl)-p-diisopropylbenzol,
  • α.α'- Bis-(4-hydroxyphenyl)-m-diisopropylbenzol,
  • Bis-(4-hydroxyphenyl)sulfon,
  • Bis-(4-hydroxyphenyl)sulfon,
  • Bis-(4-hydroxyphenyl)methan,
  • 1,1-Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan,
  • 2,2-Bis-(2,6-dimethyl-4-hydroxyphenyl)propan,
  • 2,2-Bis-(4-hydroxyphenyl)hexafluorpropan,
  • 1,1-(4-Hydroxyphenyl)-1-phenylethan,
  • Bis-(4-Hydroxyphenyl)diphenylmethan,
  • Dihydroxydiphenylether,
  • 4,4'-Thiobisphenol,
  • 1,1-Bis-(4-Hydroxyphenyl)-1-(1-naphthyl)ethan,
  • 1,1-Bis-(4-Hydroxyphenyl)-1-(2-naphthyl)ethan,
  • 2,3-Dihydroxy-3-(4-hydroxyphenyl)-1,1,3-trimethyl-1H-inden-5-ol,
  • 2,3-Dihydroxy-1-(4-hydroxyphenyl)-1,3,3-trimethyl-1H-inden-5-ol,
  • 2,2',3,3'-Tetrahydro-3,3,3',3'-tetramethyl-1,1'-Spirobi[1H-inden]-5,5'-diol.
  • Besonders bevorzugt sind
  • Resorcin,
  • 1,1-Bis-(4-Hydroxyphenyl)-1-(1-naphthyl)ethan,
  • 1,1-Bis-(4-Hydroxyphenyl)-1-(2-naphthyl)ethan,
  • 2,2-Bis-(4-hydroxyphenyl)propan,
  • α,α'- Bis-(4-hydroxyphenyl)-p-diisopropylbenzol,
  • α,α'- Bis-(4-hydroxyphenyl)-m-diisopropylbenzol,
  • 1,1-Bis-(4-hydroxyphenyl)cyclohexan,
  • 1,1-Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan,
  • Bis-(4-Hydroxyphenyl)diphenylmethan,
  • 4,4'-Dihydroxydiphenyl.
Preferred diphenols are, for example:
  • 4,4'-dihydroxydiphenyl,
  • 2,2-bis (4-hydroxyphenyl) propane,
  • 2,4-bis (4-hydroxyphenyl) -2-methylbutane,
  • 1,1-bis (4-hydroxyphenyl) cyclohexane,
  • 1,1-bis (4-hydroxyphenyl) -4-methylcyclohexane,
  • α, α'-bis- (4-hydroxyphenyl) -p-diisopropylbenzene,
  • α, α'-bis- (4-hydroxyphenyl) -m-diisopropylbenzene,
  • sulfone bis (4-hydroxyphenyl)
  • sulfone bis (4-hydroxyphenyl)
  • methane bis (4-hydroxyphenyl)
  • 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
  • 2,2-bis- (2,6-dimethyl-4-hydroxyphenyl) propane,
  • 2,2-bis (4-hydroxyphenyl) hexafluoropropane,
  • 1,1- (4-hydroxyphenyl) -1-phenylethane,
  • Bis (4-hydroxyphenyl) diphenylmethane,
  • dihydroxydiphenyl,
  • 4,4'-thiobisphenol,
  • 1,1-bis (4-hydroxyphenyl) -1- (1-naphthyl) ethane,
  • 1,1-bis (4-hydroxyphenyl) -1- (2-naphthyl) ethane,
  • 2,3-dihydroxy-3- (4-hydroxyphenyl) -1,1,3-trimethyl-1 H- inden-5-ol,
  • 2,3-dihydroxy-1- (4-hydroxyphenyl) -1,3,3-trimethyl-1 H -inden-5-ol,
  • 2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi [1H-indene] -5,5'-diol.
  • Particularly preferred
  • resorcinol,
  • 1,1-bis (4-hydroxyphenyl) -1- (1-naphthyl) ethane,
  • 1,1-bis (4-hydroxyphenyl) -1- (2-naphthyl) ethane,
  • 2,2-bis (4-hydroxyphenyl) propane,
  • α, α'-bis- (4-hydroxyphenyl) -p-diisopropylbenzene,
  • α, α'-bis- (4-hydroxyphenyl) -m-diisopropylbenzene,
  • 1,1-bis (4-hydroxyphenyl) cyclohexane,
  • 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
  • Bis (4-hydroxyphenyl) diphenylmethane,
  • 4,4'-dihydroxydiphenyl.

Verzweiger sind die für die Polycarbonatherstellung geeigneten Verbindungen mit drei und mehr funktionellen Gruppen, vorzugsweise solche mit drei oder mehr als drei phenolischen OH-Gruppen. Beispiele für geeignete Verzweiger sind Phloroglucin,

  • 4,6-Dimethyl-2,4,6-tri-(4-hydroxyphenyl)heptan,
  • 1,3,5-Tri-(4-hydroxyphenyl)benzol,
  • 1,1,1-Tri-(4-hydroxyphenyl)ethan,
  • Tri-(4-hydroxyphenyl)phenylmethan,
  • 2,2-Bis-[4,4-bis(4-hydroxyphenyl)cyclohexyl]propan,
  • 2,4-Bis-(4-hydroxyphenyl-isopropyl)phenol,
  • 2,6-Bis-(2-hydroxy-5-methylbenzyl)-4-methylphenol,
  • 2-(4-H-ydroxyphenyl)-2-(2,4-dihydroxyphenyl)propan,
  • Hexa-[4-(4-hydroxyphenyl-isopropyl)phenyl]orthoterephthalsäureester,
  • Tetra-(4-hydroxyphenyl)methan,
  • Tetra-[4-(4-hydroxyphenyl-isopropyl)phenoxy]methan,
  • 1,4-Bis-[4',4"-dihydroxytriphenyl)methyl]benzol,
  • α,α',α"-Tris-(4-hydroxyphenyl)-1,3,4-triisopropenylbenzol,
  • Isatinbiskresol,
  • Pentaerythrit,
  • 2,4-Dihydroxybenzoesäure,
  • Trimesinsäure,
  • Cyanursäure.
Branches are the polycarbonate-producing compounds having three or more functional groups, preferably those having three or more than three phenolic OH groups. Examples of suitable branching agents are phloroglucinol,
  • 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane,
  • 1,3,5-tri- (4-hydroxyphenyl) benzene,
  • 1,1,1-tri- (4-hydroxyphenyl) ethane,
  • Tri- (4-hydroxyphenyl) phenylmethane;
  • 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane,
  • 2,4-bis (4-hydroxyphenyl-isopropyl) phenol,
  • 2,6-bis- (2-hydroxy-5-methylbenzyl) -4-methylphenol,
  • 2- (4-H-ydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane;
  • Hexa- [4- (4-hydroxyphenyl-isopropyl) phenyl] orthoterephthalsäureester,
  • methane tetra (4-hydroxyphenyl)
  • Tetra- [4- (4-hydroxyphenyl-isopropyl) phenoxy] methane,
  • 1,4-bis- [4 ', 4 "-dihydroxytriphenyl) methyl] benzene,
  • α, α ', α "-tris (4-hydroxyphenyl) -1,3,4-triisopropenyl benzene,
  • isatinbiscresol,
  • pentaerythritol,
  • 2,4-dihydroxybenzoic acid,
  • trimesic
  • Cyanuric acid.

Besonders bevorzugt sind 1,1,1-Tri-(4-hydroxyphenyl)-ethan und Isatinbiskresol.Particularly preferred are 1,1,1-tri- (4-hydroxyphenyl) ethane and isatin biscresol.

Das erfindungsgemäße Verfahren wird allgemein bei Temperaturen zwischen 75°C bis 325°C und Drücken von 1 bar bis 0,01 mbar ausgeführt.The inventive method is generally carried out at temperatures between 75 ° C to 325 ° C and pressures of 1 bar to 0.01 mbar.

Die Durchführung des erfindungsgemäßen Verfahrens erfolgt beispielsweise derart, daß in der ersten Stufe das Aufschmelzen der Diphenole, der Kohlensäurediester, des Katalysators und gegebenenfalls der Alkylphenole und Verzweiger bei Temperaturen von 75°C bis 225°C, vorzugsweise von 105°C bis 235°C, besonders bevorzugt von 120°C bis 190°C, unter normalem Druck in 0,1 bis 5 Stunden, bevorzugt in 0,25 bis 3 Stunden erfolgt. Dann wird durch Anlegen von Vakuum und Erhöhung der Temperatur durch Abdestillieren des Monophenols das Oligocarbonat hergestellt. Im letzen Schritt wird bei der Polykondensation durch weiteres Erhöhen der Temperatur auf 240°C bis 325°C und bei einem Druck von <2 mbar das Polycarbonat hergestellt.The implementation of the method according to the invention is carried out, for example, such that in the first stage, the melting of the diphenols, the carbonic diester, the Catalyst and optionally the alkylphenols and branching agents at temperatures from 75 ° C to 225 ° C, preferably from 105 ° C to 235 ° C, more preferably from 120 ° C to 190 ° C, under normal pressure in 0.1 to 5 hours, preferably in 0.25 to 3 hours. Then, by applying a vacuum and raising the temperature by distilling off the monophenol, the oligocarbonate is prepared. In the last step, the polycarbonate is prepared by further increasing the temperature to 240 ° C to 325 ° C and at a pressure of <2 mbar in the polycondensation.

Das erfindungsgemäße Verfahren kann sowohl kontinuierlich als auch diskontinuierlich durchgeführt werden, und zwar beispielsweise in Rührkesseln, Dünnschichtverdampfern, Rührkesselkaskaden, Extrudern, Knetern, einfachen Scheibenreaktoren oder Hochviskosreaktoren.The process according to the invention can be carried out both continuously and discontinuously, for example in stirred vessels, thin-film evaporators, stirred tank cascades, extruders, kneaders, simple disk reactors or high-viscosity reactors.

Die Isolierung der erfindungsgemäß erhältlichen Polycarbonate erfolgt beispielsweise durch Austragen, Abspinnen und Granulierung.The isolation of the polycarbonates obtainable according to the invention takes place, for example, by discharging, spinning and granulation.

Die nach dem erfindungsgemäßen Verfahren erhältlichen Polycarbonate können Gewichtsmittelmolekulargewichte Mw zwischen etwa 2 000 und 150 000, vorzugsweise zwischen etwa 4 500 und 55 000 haben, wobei Mw über die relative Lösungsviskosität in Dichlormethan oder in Mischungen gleicher Gewichtsmengen Phenol/o-Dichlorbenzol ermittelt wird, wobei die Eichung durch Lichtstreuung erfolgt.The polycarbonates obtainable by the process according to the invention may have weight average molecular weights M w between about 2,000 and 150,000, preferably between about 4,500 and 55,000, wherein M w is determined by the relative solution viscosity in dichloromethane or mixtures of equal amounts by weight phenol / o-dichlorobenzene wherein the calibration is done by light scattering.

Die erfindungsgemäß erhältlichen Polycarbonate weisen die üblichen literaturbekannten OH-Endgruppengehalte auf, die photometrisch mit Titantetrachlorid ermittelt werden können.The polycarbonates obtainable according to the invention have the usual OH end group contents known from the literature, which can be determined photometrically with titanium tetrachloride.

Die nach dem erfindungsgemäßen Verfahren hergestellten Polycarbonate zeigen gute mechanische Eigenschaften, hohe Transparenz und sind frei von Lösungsmitteln.The polycarbonates produced by the process of the invention show good mechanical properties, high transparency and are free of solvents.

Der Einbau der eingesetzten Alkylphenole wurde bei Cumylphenol durch 13C-, bei den anderen Alkylphenolen durch 1H-NMR-Spektroskopie ermittelt. Daraus wurde errechnet, wieviel Prozent des eingesetzten Kettenabbrechers im Polycarbonat als Endgruppe vorlag.The incorporation of the alkylphenols used was determined by 13 C for cumylphenol, and by 1 H-NMR spectroscopy for the other alkylphenols. That became calculated how many percent of the chain terminator used was present in the polycarbonate as an end group.

Zur Verbesserung der Eigenschaften können den erfindungsgemäß hergestellten Polycarbonaten Hilfs- und Verstärkungsstoffe zugemischt werden. Als solche sind u. a. in Betracht zu ziehen: Stabilisatoren, Fließhilfsmittel, Entformungsmittel, Brandschutzmittel, Pigmente, fein zerteilte Mineralien, Faserstoffe, Thermostabilisatoren wie z. B. Alkyl- und Arylphosphite, -phosphate, -phosphane, niedermolekulare Carbonsäureester, Halogenverbindungen, Salze, Kreide, Quarzmehl, Glas- und Kohlenstoffasern, Pigmente und deren Kombinationen.In order to improve the properties, auxiliaries and reinforcing materials can be added to the polycarbonates prepared according to the invention. As such, u. a. to be considered: stabilizers, flow aids, mold release agents, fire retardants, pigments, finely divided minerals, fibrous materials, heat stabilizers such. As alkyl and aryl phosphites, phosphates, phosphanes, low molecular weight carboxylic acid esters, halogen compounds, salts, chalk, quartz powder, glass and carbon fibers, pigments and combinations thereof.

Weiterhin können den erfindungsmäßen Polycarbonaten auch andere Polymere zugemischt werden, z. B. Polyolefine, Polyurethane, Polyester und Polystyrol.Furthermore, the erfindungsmäßen polycarbonates and other polymers can be admixed, for. As polyolefins, polyurethanes, polyesters and polystyrene.

Der Zusatz dieser Stoffe erfolgt vorzugsweise auf herkömmlichen Aggregaten zum fertigen Polycarbonat, kann jedoch, je nach den Erfordernissen, auf einer anderen Stufe des erfindungsgemäßen Verfahrens erfolgen.The addition of these substances is preferably carried out on conventional aggregates for the finished polycarbonate, but may, depending on the requirements, take place at another stage of the process according to the invention.

Die nach dem erfindungsgemäßen Verfahren erhältlichen Polycarbonate können auf üblichen Maschinen, beispielsweise auf Extrudern oder Spritzgußmaschinen zu beliebigen Formkörpern, beispielsweise zu Folien oder Platten in üblicher Weise verarbeitet werden.The polycarbonates obtainable by the process according to the invention can be processed on conventional machines, for example on extruders or injection molding machines to form any shaped articles, for example into films or plates in a conventional manner.

Der technische Einsatz dieser Polycarbonatfomikörper kann beispielsweise in der Optik und in der Elektrotechnik erfolgen.The technical use of these Polycarbonatfomikörper can be done for example in optics and in electrical engineering.

BeispieleExamples Vergleichsbeispiel 1Comparative Example 1

In einem 500 ml Dreihalskolben mit Rührer, Innenthermometer und Vigreuxkolonne (30 cm, verspiegelt) mit Brücke werden 45,60 g (0,2 mol) Bisphenol A, 47,08 g (110 mol% bezogen auf Bisphenol A) Diphenylcarbonat, 3,7 mg (0,03 mol% bezogen auf Bisphenol A) Borsäure und 2,12 g (5 mol% bezogen auf Bisphenol A) 4-Cumylphenol eingewogen. Die Apparatur wird durch Anlegen von Vakuum und Spülen mit Stickstoff (dreimal) vom Luftsauerstoff befreit und das Gemisch bei 180°C aufgeschmolzen und 30 Minuten gerührt. Anschließend werden 36,5 mg (0,03 mol% bezogen auf Bisphenol A) einer 15%igen Ammoniumhydroxid-Lösung und 0,5 mg (0,003 mol% bezogen auf Bisphenol A) Natriumhydrogencarbonat zugegeben und weitere 30 Minuten gerührt. Die Temperatur wird auf 210°C und das Vakuum auf 200 mbar erhöht und das entstehende Phenol abdestilliert. Nach 1 Stunde wird die Temperatur auf 240°C erhöht und nach 20 Minuten das Vakuum auf 150 mbar verbessert. Nach weiteren 20 Minuten wird der Druck auf 100 mbar erniedrigt und 20 Minuten gehalten. Anschließend wird für 30 Minuten der Druck auf 15 mbar reduziert. Nun wird die Temperatur auf 270°C erhöht, das Vakuum auf 0,5 mbar verbessert und nochmals 2 Stunden gerührt. Die Ergebnisse sind in Tabelle 1 zusammengefaßt.In a 500 ml three-necked flask with stirrer, internal thermometer and Vigreux column (30 cm, mirrored) with bridge are 45.60 g (0.2 mol) of bisphenol A, 47.08 g (110 mol% based on bisphenol A) of diphenyl carbonate, 3, 7 mg (0.03 mol% based on bisphenol A) boric acid and 2.12 g (5 mol% based on bisphenol A) 4-cumylphenol weighed. The apparatus is freed from atmospheric oxygen by applying a vacuum and purging with nitrogen (three times) and the mixture is melted at 180 ° C. and stirred for 30 minutes. Subsequently, 36.5 mg (0.03 mol% based on bisphenol A) of a 15% ammonium hydroxide solution and 0.5 mg (0.003 mol% based on bisphenol A) of sodium bicarbonate are added and the mixture is stirred for a further 30 minutes. The temperature is raised to 210 ° C and the vacuum to 200 mbar and the resulting phenol distilled off. After 1 hour, the temperature is increased to 240 ° C and after 20 minutes, the vacuum improved to 150 mbar. After a further 20 minutes, the pressure is lowered to 100 mbar and held for 20 minutes. Subsequently, the pressure is reduced to 15 mbar for 30 minutes. Now the temperature is increased to 270 ° C, the vacuum improved to 0.5 mbar and stirred again for 2 hours. The results are summarized in Table 1.

Vergleichsbeispiel 2Comparative Example 2

Wie Vergleichsbeispiel 1, nur werden 22 mg (0,03 mol% bezogen auf Bisphenol A) einer 25%igen Ammoniumhydroxid-Lösung und 5 mg (0,0003 mol% bezogen auf Bisphenol A) einer 1%igen Natriumhydrogencarbonat-Lösung zugegeben. Die Ergebnisse sind in Tabelle 1 zusammengefaßt.As Comparative Example 1, only 22 mg (0.03 mol% based on bisphenol A) of a 25% ammonium hydroxide solution and 5 mg (0.0003 mol% based on bisphenol A) of a 1% sodium bicarbonate solution are added. The results are summarized in Table 1.

Vergleichsbeispiel 3Comparative Example 3

In einem 500 ml Dreihalskolben mit Rührer, Innenthermometer und Vigreuxkolonne (30 cm, verspiegelt) mit Brücke werden 45,66 g (0,2 mol) Bisphenol A, 47,13 g (110 mol% bezogen auf Bisphenol A) Diphenylcarbonat, 22 mg (0,03 mol% bezogen auf Bisphenol A) einer 25%igen Ammoniumhydroxid-Lösung, 5 mg (0,0003 mol% bezogen auf Bisphenol A) einer 1%igen Natriumhydrogencarbonat-Lösung und 2,12. g (5 mol% bezogen auf Bisphenol A) 4-Cumylphenol eingewogen. Die Apparatur wird durch Anlegen von Vakuum und Spülen mit Stickstoff (dreimal) vom Luftsauerstoff befreit und das Gemisch bei 150°C aufgeschmolzen. Die Temperatur wird auf 190°C und das Vakuum auf 100 mbar erhöht und das entstehende Phenol abdestilliert. Nach 20 Minuten wird die Temperatur auf 235°C erhöht und das Vakuum auf 60 mbar verbessert. Nach 15 Minuten wird die Temperatur auf 250°C und nach weiteren 15 Minuten das Vakuum auf 5 mbar erhöht. Anschließend wird auf 280°C aufgeheizt und der Druck nach 15 Minuten auf 0,5 mbar reduziert. Nach wiederum 15 Minuten wird bei 300°C nochmals 30 Minuten gerührt. Die Ergebnisse sind in Tabelle 1 zusammengefaßt. Tabelle 1 Vergleichsbeispiel Lösungsviskosität eingesetztes Alkylphenol [mol%] gefundenes Alkylphenol [mol%] Einbau des Alkylphenols [%] 1 1,142 5 3,7 74 2 1,167 5 3,5 75 3 1,146 5 3,8 76 In a 500 ml three-necked flask equipped with stirrer, internal thermometer and Vigreux column (30 cm, mirrored) with bridge are 45.66 g (0.2 mol) of bisphenol A, 47.13 g (110 mol% based on bisphenol A) of diphenyl carbonate, 22 mg (0.03 mol% based on bisphenol A) of a 25% ammonium hydroxide solution, 5 mg (0.0003 mol% based on bisphenol A) of a 1% sodium bicarbonate solution and 2.12. g (5 mol% based on bisphenol A) 4-cumylphenol weighed. The apparatus is freed from atmospheric oxygen by applying a vacuum and purging with nitrogen (three times) and the mixture is melted at 150 ° C. The temperature is raised to 190 ° C and the vacuum to 100 mbar and the resulting phenol distilled off. After 20 minutes, the temperature is increased to 235 ° C and the vacuum improved to 60 mbar. After 15 minutes, the temperature is raised to 250 ° C and after a further 15 minutes, the vacuum to 5 mbar. The mixture is then heated to 280 ° C and the pressure after 15 minutes reduced to 0.5 mbar. After another 15 minutes, stirred at 300 ° C for another 30 minutes. The results are summarized in Table 1. <b> Table 1 </ b> Comparative example solution viscosity used alkylphenol [mol%] Found alkylphenol [mol%] Incorporation of the alkylphenol [%] 1 1,142 5 3.7 74 2 1,167 5 3.5 75 3 1,146 5 3.8 76

Beispiel 1example 1

Wie Vergleichsbeispiel 2, nur werden statt Tetramethylammoniumhydroxid 4,9 mg (0,004 mol% bezogen auf Bisphenol A) Tetraphenylphosphoniumphenolat (wird als Mischkristall mit 30 Gew.% Phenol bezogen auf den Mischkristall zudosiert) zugegeben. Auf die Zugabe von Natriumhydrogencarbonat wird verzichtet. Die Ergebnisse sind in Tabelle 2 zusammengefaßt.Like Comparative Example 2, only 4.9 mg (0.004 mol% based on bisphenol A) of tetraphenylphosphonium phenolate (added as mixed crystal with 30% by weight of phenol, based on the mixed crystal) are added instead of tetramethylammonium hydroxide. The addition of sodium bicarbonate is omitted. The results are summarized in Table 2.

Beispiel 2Example 2

Wie Beispiel 1, es wird jedoch auf die Zugabe von Borsäure verzichtet. Die Ergebnisse sind in Tabelle 2 zusammengefaßt.As Example 1, but it is dispensed with the addition of boric acid. The results are summarized in Table 2.

Beispiel 3Example 3

Wie Vergleichsbeispiel 3, nur werden 45,66 g (0,2 mol) Bisphenol A, 46,21 g (108 mol% bezogen auf Bisphenol A) Diphenylcarbonat, 4,9 mg (0,004 mol% bezogen auf Bisphenol A) Tetraphenylphosphoniumphenolat (wird als Mischkristall mit 30 Gew.% Phenol bezogen auf den Mischkristall zudosiert) und 1,49 g (4 mol% bezogen auf Bisphenol A) 4-Phenoxyphenol eingewogen.As Comparative Example 3, only 45.66 g (0.2 mol) of bisphenol A, 46.21 g (108 mol% based on bisphenol A) of diphenyl carbonate, 4.9 mg (0.004 mol% based on bisphenol A) Tetraphenylphosphoniumphenolat (wird as mixed crystal with 30 wt.% Phenol based on the mixed crystal added) and 1.49 g (4 mol% based on bisphenol A) 4-phenoxyphenol weighed.

Beispiel 4Example 4

Wie Beispiel 3, nur werden 45,84 g (107 mol% bezogen auf Bisphenol A) Diphenylcarbonat und 1,22 g (2 mol% bezogen auf Bisphenol A) 3-Pentadecylphenol statt 4-Phenoxyphenol eingewogen.As Example 3, only 45.84 g (107 mol% based on bisphenol A) diphenyl carbonate and 1.22 g (2 mol% based on bisphenol A) of 3-pentadecylphenol instead of 4-phenoxyphenol weighed.

Beispiel 5Example 5

Wie Beispiel 3, nur werden 45,41 g (106 mol% bezogen auf Bisphenol A) Diphenylcarbonat und statt 4-Phenoxyphenol 3,32 g (5 mol% bezogen auf Bisphenol A) Cumylphenylphenylcarbonat eingewogen. Die Ergebnisse sind in Tabelle 2 zusammengefaßt. Tabelle 2 Beispiel Lösungsviskosität eingesetztes Alkylphenol [mol%] gefundenes Alkylphenol [mol%] Einbau des Alkylphenols [%] 1 1,134 5 4,0 80 2 1,160 5 4,2 84 3 1,158 4 3,2 80 4 1,161 2 2,0 100 5 1,113 5 4,2 84 As in Example 3, only 45.41 g (106 mol% based on bisphenol A) of diphenyl carbonate and instead of 4-phenoxyphenol 3.32 g (5 mol% based on bisphenol A) Cumylphenylphenylcarbonate weighed. The results are summarized in Table 2. <u> Table 2 </ u> example solution viscosity used alkylphenol [mol%] Found alkylphenol [mol%] Incorporation of the alkylphenol [%] 1 1,134 5 4.0 80 2 1,160 5 4.2 84 3 1,158 4 3.2 80 4 1,161 2 2.0 100 5 1,113 5 4.2 84

Claims (7)

  1. Process for the preparation of polycarbonates by the melt transesterification process from a single bisphenol and a carbonic acid diester in the presence of a phenol which is substituted by alkyl groups and is suitable as a chain terminator, wherein the phenol used as the chain terminator can be employed in the free form or as a compound which is capable of transesterification under the synthesis conditions, characterized in that phosphonium salts of the formula (I)
    Figure imgb0008
     wherein
    R1-4 are identical or different and denote methyl or C6-C14-aryl and
    X- is an anion,
    are employed as a catalyst and 80 % or more of the phenol employed as the chain terminator is incorporated into the polycarbonate.
  2. Process according to claim 1, characterized in that the phosphonium catalyst is employed in concentrations of from 10-2 mol to 10-6 mol, based on 1 mol of diphenol.
  3. Process according to claim 1 or 2, characterized in that the catalyst used is tetraphenylphosphonium phenolate.
  4. Process according to claim 1, wherein X- is sulfate, bisulfate, bicarbonate, carbonate, acetate, boranate, hydrogen phosphate, halide or an alcoholate of the formula OR, wherein R is C6-C14-aryl or C7-C12-aralkyl.
  5. Process according to claim 4, wherein the bisphenol is bisphenol A.
  6. Process according to one of the abovementioned claims, characterized in that the phenol used as the chain terminator is employed in amounts of 0.4 - 17 mol%, preferably 1.3 - 8.6 mol%, based on the bisphenol.
  7. Process according to claim 1, characterized in that the chain terminator is tritylphenol, cumylphenol, phenoxyphenol or pentadecylphenol.
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